CN107068869A - A kind of perovskite/organic integration solar cell and preparation method thereof - Google Patents

A kind of perovskite/organic integration solar cell and preparation method thereof Download PDF

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Publication number
CN107068869A
CN107068869A CN201710270486.4A CN201710270486A CN107068869A CN 107068869 A CN107068869 A CN 107068869A CN 201710270486 A CN201710270486 A CN 201710270486A CN 107068869 A CN107068869 A CN 107068869A
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layer
perovskite
light absorbing
organic
prepared
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谭占鳌
郭强
李聪
史珍珍
白鸣
白一鸣
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North China Electric Power University
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North China Electric Power University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a kind of perovskite/organic integration solar cell and preparation method thereof.Its structure of described perovskite/organic integration solar cell includes transparency electrode, charge transport layer, perovskite light absorbing layer, organic light absorbing layer and metal electrode from bottom to top.Using this battery, the light of short wavelength is mainly absorbed by calcium titanium ore bed, and the light of long wavelength is utilized by organic light absorbing layer.Utilization of the battery to sunshine can be effectively improved by preparing such a integrated battery, compared to single battery, effectively improve utilization of the battery to sunshine.Meanwhile, compared to conventional laminated cell, front and rear sub- battery does not need any intermediate connecting layer in perovskite/organic integration solar cell, enormously simplify the preparation process and technique of device, adds the repeatability between batch, be conducive to industrialized production.

Description

A kind of perovskite/organic integration solar cell and preparation method thereof
Technical field
The invention belongs to novel thin film solar cell material and device arts, and in particular to a kind of perovskite/organic Integrated solar cell and preparation method thereof.
Background technology
The perovskite solar cell of rising in recent years, because its have simple in construction, efficiency high, cost it is low, can solution add The advantages of work and as novel thin film solar cell field study hotspot.The development of perovskite solar cell is very rapid, short Short several years battery efficiencies are by being initially reported less than 4% lifting till now more than 22%.Sunshine reaches the energy of earth surface Amount is concentrated mainly on 350-1500nm, and in perovskite battery, now the most frequently used CsPbI3、CH3NH3PbI3And H2C(NH2)2PbI3ABSORPTION EDGE be respectively 720,800 and 850nm, still there is most sunshine not to be utilized.Organic conjugate material By Molecular Design absorption spectrum can be realized more than 1000nm.Using organic conjugate material and perovskite material to light Complementary absorption, can widen the spectral absorption scope of perovskite/organic integration solar cell, improve the utilization rate of sunshine, enter And lift the energy conversion efficiency of solar cell.In integrated morphology solar cell, closed according to the size of material energy gap The position of assembled arrangement in the devices is managed, allows the shorter light of wavelength to be absorbed by the perovskite material of broad-band gap, wavelength is longer Luminous energy penetrate calcium titanium ore bed, absorbed by the organic conjugate material of narrow band gap, former and later two batteries are joined together just can be real Now sunshine is farthest absorbed.
In order at utmost absorb sunshine, the method most generally taken at present is to prepare stacked solar cell, cascade solar cell, however, folded The quality in the intermediate layer in layer battery is very big to the performance impact of battery, and needs to consider the anti-of intermediate layer in preparation process The problems such as solvent borne, wellability, level-density parameter, considerably increase the preparation difficulty of device.Perovskite/organic integration solar cell In before and after sub- battery do not need any intermediate connecting layer, enormously simplify the preparation process and technique of device, add between batch Repeatability, be conducive to industrialized production.
The content of the invention
The invention provides a kind of perovskite/organic integration solar cell and preparation method thereof, compared to lamination sun electricity Pond, the sub- battery complementary absorption sunshine before and after ensureing, while increasing the utilization of light, the front and rear sub- battery in integrated battery is not Any intermediate connecting layer is needed, the preparation process and technique of device is enormously simplify.
The perovskite/organic integration solar cell has two kinds of typical device architectures, and concrete technical scheme is as follows：
A kind of perovskite/organic integration solar cell, it is characterised in that its structure includes from bottom to top：Transparency electrode, electricity Lotus transport layer, perovskite light absorbing layer, organic light absorbing layer and metal electrode.
Described charge transport layer can be electron transfer layer (n-type metal oxide or n-type organic material), or Hole transmission layer (p-type metal oxide or p-type organic material).
The device architecture is that transparency electrode/electron transfer layer/perovskite light absorbing layer/organic light absorbing layer/hole is passed Defeated layer/metal electrode；Or transparency electrode/hole transmission layer/perovskite light absorbing layer/organic light absorbing layer/electron transfer layer/gold Belong to electrode.
The absorption spectrum of described organic light absorbing layer is wider than the absorption spectrum of perovskite light absorbing layer, is organic narrow band gap Class material.
When the charge transport layer is electron transfer layer, described metal electrode is high work function metal；When the electric charge When transport layer is hole transmission layer, described metal electrode is low work function metal.
A kind of preparation method of perovskite/organic integration solar cell, method one comprises the following steps：
A. transparent conductive metal oxide anode layer is prepared：Splash-proofing sputtering metal is aoxidized on the substrate of glass or polyester film Thing, obtains transparent conductive metal oxide anode layer；
B. hole transmission layer is prepared：The transparent conductive metal oxide anode layer that step a is obtained is through ultraviolet-ozone table The organic material or metal oxide of spin coating high work content, hole transmission layer is obtained through thermal annealing after the processing of face；
C. perovskite light absorbing layer is prepared：Lead source and iodide are dissolved in solvent, heating stirring obtains body before perovskite Liquid solution, the solution is spun on the hole transmission layer that step b is obtained, perovskite light absorbing layer is obtained through thermal annealing；
D. organic light absorbing layer is prepared:P-type organic material and N-type organic material are mixed in proportion be dissolved in solvent be made it is molten Liquid, the solution is spun on calcium titanium ore bed and obtains organic light absorbing layer；
E. electron transfer layer is prepared：Prepared on organic light-absorption layer that step d is obtained by the method for spin coating or evaporation low Work content is organic or metal oxide electron transport layer；
F. cathode layer is prepared：Vacuum evaporation metal electrode, is used as cathode layer on the electron transfer layer that step e is obtained；
Method two comprises the following steps：：
A. transparent conductive metal oxide anode layer is prepared：Splash-proofing sputtering metal is aoxidized on the substrate of glass or polyester film Thing, obtains transparent conductive metal oxide-coated cathode layer；
B. electron transfer layer is prepared：By n-type metal oxide it is spin-coated or be sprayed at transparent conductive cathode layer on, through high temperature Electron transfer layer is obtained after annealing；
C. perovskite light absorbing layer is prepared：Lead source and iodide are dissolved in solvent, heating stirring obtains body before perovskite Liquid solution, the solution is spun on the electron transfer layer that step b is obtained, perovskite light absorbing layer is obtained through thermal annealing；
D. organic light absorbing layer is prepared:P-type organic material and N-type organic material are mixed in proportion be dissolved in solvent be made it is molten Liquid, the solution is spun on calcium titanium ore bed and obtains organic light absorbing layer；
E. hole transmission layer is prepared：Original text is prepared by the method for spin coating or evaporation on organic light-absorption layer that step d is obtained The organic or metal oxide hole transmission layer of work content；
F. anode layer is prepared：Vacuum evaporation metal electrode, is used as anode layer on the hole transmission layer that step e is obtained.
Further, organic material is PEDOT described in the step b of method one：PSS.
Further, by PbI in method one or illegal two steps c2:DMSO mass ratioes are 1:1, DMF concentration is dissolved in for 1M, rotation Painting rotating speed is 5000rpm, CH3NH3I or H2C(NH2)2I aqueous isopropanol concentration is respectively 50mg/ml and 68mg/ml, spin coating Rotating speed is 5000rpm；Or by PbI21 is pressed with CsI:1 ratio is mixed to prepare precursor solution, then after a step spin-coating method 100 DEG C of annealing obtain CsPbI3Perovskite light absorbing layer.
Further, by TTV2 and PC in method one or the step d of method two70BM is described molten by necessarily solvent is dissolved in than mixing Agent is chloroform and o-dichlorohenzene, or by PBDTTT-E-T and IEICO by being necessarily dissolved in solvent than mixing that precursor is made is molten Liquid, the solvent is chlorobenzene, and resulting solution is spun on the calcium titanium ore bed that step c is obtained and obtains organic polymer light absorbs Layer.
Further, the n-butanol of 0.15M titanium acetylacetones is spun in transparency electrode in the step b of method two, 125 DEG C are moved back 5~10min of fire, is then spin coated onto TiO2Casing play solution, then by 550 DEG C sintering 30min prepare TiO2Electric transmission Layer.
Specifically：
Device architecture one：Transparency electrode/hole transmission layer/calcium titanium ore bed/organic light-absorption layer/electron transfer layer/metal electricity Pole
A. transparent conductive metal oxide anode layer is prepared：Splash-proofing sputtering metal is aoxidized on the substrate of glass or polyester film Thing, obtains transparent conductive metal oxide anode layer；
B. hole transmission layer is prepared：The transparent conductive metal oxide anode layer that step a is obtained is through ultraviolet-ozone table The conducting polymer or metal oxide of spin coating high work content, hole transmission layer is obtained through thermal annealing after the processing of face；
C. perovskite light absorbing layer is prepared：By PbI2DMF solvent is dissolved in DMSO, by CH3NH3I or H2C(NH2)2I's is different Propanol solution, CH is obtained by two step spin-coating methods3NH3PbI3Or H2C(NH2)2PbI3Perovskite light absorbing layer or by PbI2With CsI presses 1:1 ratio is mixed to prepare precursor solution, and then 100 DEG C of annealing obtain CsPbI after a step spin-coating method3Perovskite Light absorbing layer.
D. organic polymer light absorbing layer is prepared:By TTV2 and PC70BM, or will by being necessarily dissolved in solvent than mixing PBDTTT-E-T and IEICO than mixing by being necessarily dissolved in solvent precursor solution being made, and resulting solution is spun on into step c obtains To calcium titanium ore bed on obtain organic polymer light absorbing layer；
E. cathode layer is prepared：Vacuum evaporation metal electrode, is used as cathode layer on the electron transfer layer that step d is obtained.
Device architecture two：Transparency electrode/electron transfer layer/calcium titanium ore bed/organic light-absorption layer/hole transmission layer/metal electricity Pole
A. transparent conductive metal oxide anode layer is prepared：Splash-proofing sputtering metal is aoxidized on the substrate of glass or polyester film Thing, obtains transparent conductive metal oxide-coated cathode layer；
B. electron transfer layer is prepared：The n-butanol of 0.15M titanium acetylacetones is spun in transparency electrode, 125 DEG C of annealing 5 ~10min, is then spin coated onto TiO2Casing play solution, then by 550 DEG C sintering 30min prepare TiO2Electron transfer layer；
C. perovskite light absorbing layer is prepared：By PbI2DMF solvent is dissolved in DMSO, by CH3NH3I or H2C(NH2)2I's is different Propanol solution, CH is obtained by two step spin-coating methods3NH3PbI3Or H2C(NH2)2PbI3Perovskite light absorbing layer or by PbI2With CsI is mixed to prepare precursor solution, and 100 DEG C of annealing obtain CsPbI after a step spin-coating method3Perovskite light absorbing layer..
D. organic polymer light absorbing layer is prepared:By TTV2 and PC70BM presses certain D:A is dissolved in solvent than mixing, or PBDTTT-E-T and IEICO is pressed into certain D:A is dissolved in solvent than mixing and precursor solution is made, and resulting solution is spun on Organic polymer light absorbing layer is obtained on the calcium titanium ore bed that step c is obtained；
E. anode layer is prepared：Vacuum evaporation metal electrode, is used as anode layer on the electron transfer layer that step d is obtained.
Beneficial effects of the present invention are：
Perovskite/organic integration solar cell, the light of short wavelength is mainly absorbed by calcium titanium ore bed, and the light of long wavelength Utilized by organic light absorbing layer, compared to single battery, effectively improve utilization of the battery to sunshine.Meanwhile, compared to conventional Laminated cell, former and later two sub- batteries of perovskite/organic integration solar cell are directly integrated, the connection without intermediate layer, greatly The big preparation process and technique for simplifying device.
Brief description of the drawings
Fig. 1 is the structure chart of perovskite/organic integration solar cell.
Fig. 2 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 1, institute It is FTO/PEDOT to obtain device architecture:PSS/CsPbI3/PC60BM/Al。
Fig. 3 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 2, institute It is FTO/PEDOT to obtain device architecture:PSS/CsPbI3/PBDTTT-E-T:IEICO/Al。
Fig. 4 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 3, institute It is FTO/PEDOT to obtain device architecture:PSS/CH3NH3PbI3/PC60BM/Al。
Fig. 5 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 4, institute It is FTO/PEDOT to obtain device architecture:PSS/CH3NH3PbI3/PBDTTT-E-T:IEICO/Al。
Fig. 6 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 5, institute It is FTO/PEDOT to obtain device architecture:PSS/CH3NH3PbI3/TTV2:PC70BM/Al。
Fig. 7 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 6, institute It is FTO/PEDOT to obtain device architecture:PSS/H2C(NH2)2PbI3/PC60BM/Al。
Fig. 8 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 7, institute It is FTO/PEDOT to obtain device architecture:PSS/H2C(NH2)2PbI3/PBDTTT-E-T:IEICO/Al。
Fig. 9 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 8, institute It is FTO/PEDOT to obtain device architecture:PSS/H2C(NH2)2PbI3/TTV2:PC70BM/Al。
Figure 10 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 9, Obtained device structure is FTO/TiO2/CsPbI3/Spiro-OMeTAD/Au。
Figure 11 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 10, Obtained device structure is FTO/TiO2/CsPbI3/PBDTTT-E-T:IEICO/Au。
Figure 12 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 11, Obtained device structure is FTO/TiO2/CH3NH3PbI3/Spiro-OMeTAD/Au。
Figure 13 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 12, Obtained device structure is FTO/TiO2/CH3NH3PbI3/PBDTTT-E-T:IEICO/Au。
Figure 14 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 13, Obtained device structure is FTO/TiO2/CH3NH3PbI3/TTV2:PC70BM/Au。
Figure 15 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 14, Obtained device structure is FTO/TiO2/H2C(NH2)2PbI3/Spiro-OMeTAD/Au。
Figure 16 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 15, Obtained device structure is FTO/TiO2/H2C(NH2)2PbI3/PBDTTT-E-T:IEICO/Au。
Figure 17 is the current-voltage characteristic curve and EQE characteristic curves of perovskite solar cell prepared by embodiment 16, Obtained device structure is FTO/TiO2/H2C(NH2)2PbI3/TTV2:PC70BM/Au。
Embodiment
The invention provides a kind of perovskite solar cell and preparation method thereof, below in conjunction with the accompanying drawings and specific embodiment The present invention will be further described.
A kind of perovskite/organic integration solar cell, it is characterised in that its structure includes from bottom to top：Transparency electrode 1, Charge transport layer 2, perovskite light absorbing layer 3, organic light absorbing layer 4 and metal electrode 5.
Embodiment 1 (comparative example)
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:CsI=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, CsPbI is made in the HBr for adding 30~40ul/ml3Precursor concentration is 1M.By CsPbI3 precursors It is spun on PEDOT:Rotating speed is 5000rpm, 30s on PSS hole transmission layers.Then 100 DEG C of annealing 10min obtain calcium titanium ore bed. Concentration is dissolved in chlorobenzene for 30mg/ml PCBM and stirred 5 hours, then by PC60BM solution is with 3000rpm spin coatings 30s bar Part is deposited on calcium titanium ore bed.Finally in 1x10-4Below Pa vacuum evaporations thickness does electrode for 100nm Al.Obtained device knot Structure is FTO/PEDOT:PSS/CsPbI3/PC60BM/Al, electricity of being opened a way under 100 milliwatts simulated solar light irradiation every square centimeter Press as 0.86V, short circuit current flow is 13.9mA/cm2, fill factor, curve factor is 42.6%, and conversion efficiency is 5.1%.Fig. 2 gives the device Current -voltage curve of the part under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts and the device EQE curves.
Embodiment 2
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:CsI=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, CsPbI is made in the HBr for adding 30~40ul/ml3Precursor concentration is 1M.By CsPbI3 precursors It is spun on PEDOT:Rotating speed is 5000rpm, 30s on PSS hole transmission layers.Then 100 DEG C of annealing 10min obtain calcium titanium ore bed. Concentration is pressed D for 10mg/ml PBDTTT-E-T and IEICO:A compares 1:1.25 are dissolved in chlorobenzene, and 70 DEG C of heating stirrings are obtained for 5 hours To organic polymer layers precursor solution.The precursor solution is deposited on 1300rpm spin coatings 60s condition in glove box On calcium titanium ore bed, then 100 DEG C of annealing 10min obtain organic polymer light absorbing layer.Finally in 1x10-4Below Pa vacuum evaporations Thickness does electrode for 100nm Al.Obtained device structure is FTO/PEDOT:PSS/CsPbI3/PBDTTT-E-T:IEICO/Al, Open-circuit voltage is 0.42V under 100 milliwatts simulated solar light irradiation every square centimeter, and short circuit current flow is 8.4mA/cm2, filling The factor is 39.4%, and conversion efficiency is 1.4%.Fig. 3 gives the device without light irradiation and every square centimeter through 100 milliwatts Simulated solar light irradiation under current -voltage curve and the device EQE curves.
Embodiment 3 (comparative example)
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:DMSO=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on PEDOT:PSS hole transmission layers Upper rotating speed is 5000rpm, then by 50mg/ml CH3NH3I//aqueous isopropanol is spun on PbI with 5000rpm rotating speed2On, 100 DEG C of annealing 30min obtain calcium titanium ore bed.The PC that concentration is 30mg/ml60BM, which is dissolved in chlorobenzene, to be stirred 5 hours, then will PCBM solution is deposited on calcium titanium ore bed with 3000rpm spin coatings 30s condition.Finally in 1x10-4Below Pa vacuum evaporation thickness Electrode is done for 100nm Al.Obtained device structure is FTO/PEDOT:PSS/CH3NH3PbI3/PC60BM/Al, it is every in 100 milliwatts Open-circuit voltage is 1.02V under the simulated solar light irradiation of square centimeter, and short circuit current flow is 15.1mA/cm2, fill factor, curve factor is 74.4%, conversion efficiency is 11.4%.Fig. 4 gives the device without light irradiation and through 100 milliwatts mould every square centimeter Intend the EQE curves of the current -voltage curve and the device under sunshine irradiation.
Embodiment 4
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:DMSO=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on PEDOT:PSS hole transmission layers Upper rotating speed is 5000rpm, then by 50mg/ml CH3NH3I//aqueous isopropanol is spun on PbI with 5000rpm rotating speed2On, 100 DEG C of annealing 30min obtain calcium titanium ore bed.Concentration is pressed D for 10mg/ml PBDTTT-E-T and IEICO:A compares 1:1.25 it is molten In chlorobenzene, 70 DEG C of heating stirrings obtain organic polymer layers precursor solution in 5 hours.By the precursor solution with 1300rpm Spin coating 60s condition is deposited on calcium titanium ore bed in glove box again, and then 100 DEG C of annealing 10min are had and polymer light is inhaled Receive layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does electrode for 100nm Al.Obtained device structure is FTO/PEDOT: PSS/CH3NH3PbI3/PBDTTT-E-T:IEICO/Al, electricity of being opened a way under 100 milliwatts simulated solar light irradiation every square centimeter Press as 0.66V, short circuit current flow is 5.2mA/cm2, fill factor, curve factor is 50.0%, and conversion efficiency is 1.72%.Fig. 5 gives the device Current -voltage curve of the part under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts and the device EQE curves.
Embodiment 5
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:DMSO=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on PEDOT:PSS hole transmission layers Upper rotating speed is 5000rpm, then by 50mg/ml CH3NH3I//aqueous isopropanol is spun on PbI with 5000rpm rotating speed2On, 100 DEG C of annealing 30min obtain calcium titanium ore bed.The TTV2 and PC that concentration is 10mg/ml70BM presses D:A compares 1:1.5 are dissolved in chloroform: O-dichlorohenzene=4:1 in the mixed solvent, stirring obtains organic polymer layers precursor solution in 5 hours.By the precursor solution Had and polymer light absorbed layer to be deposited in 1800rpm spin coatings 30s condition again glove box on calcium titanium ore bed.Finally exist 1x10-4Below Pa vacuum evaporations thickness does electrode for 100nm Al.Obtained device structure is FTO/PEDOT:PSS/ CH3NH3PbI3/TTV2:PC70BM/Al, open-circuit voltage is 0.77V under 100 milliwatts simulated solar light irradiation every square centimeter, Short circuit current flow is 10.5mA/cm2, fill factor, curve factor is 24.7%, and conversion efficiency is 2.0%.Fig. 6 gives the device without light Irradiation and the EQE curves through the current -voltage curve under 100 milliwatts simulated solar light irradiation every square centimeter He the device.
Embodiment 6 (comparative example)
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:DMSO=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, it is 1M that PbI2 precursors concentration, which is made,.By PbI2Precursor is spun on PEDOT:PSS hole transports Rotating speed is 5000rpm on layer, then 70 DEG C of annealing 10min.Then by 68mg/ml H2C(NH2)2I aqueous isopropanols with 5000rpm rotating speed is spun on PbI2, and 150 DEG C of annealing 30min obtain calcium titanium ore bed.Concentration is molten for 30mg/ml PCBM Stirred 5 hours in chlorobenzene, then by PC60BM solution is deposited on calcium titanium ore bed with 3000rpm spin coatings 30s condition.Finally In 1x10-4Below Pa vacuum evaporations thickness does electrode for 100nm Al.Obtained device structure is FTO/PEDOT:PSS/H2C (NH2)2PbI3/ PCBM/Al, open-circuit voltage is 0.92V, short circuit electricity under 100 milliwatts simulated solar light irradiation every square centimeter Flow for 18.1mA/cm2, fill factor, curve factor is 52.5%, and conversion efficiency is 8.72%.Fig. 7 gives the device without light irradiation With the EQE curves through the current -voltage curve under 100 milliwatts simulated solar light irradiation every square centimeter He the device.
Embodiment 7
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:DMSO=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on PEDOT:PSS hole transmission layers Upper rotating speed is 5000rpm, then 70 DEG C of annealing 10min.Then by 68mg/ml H2C(NH2)2I aqueous isopropanols are with 5000rpm Rotating speed be spun on PbI2On, 150 DEG C of annealing 30min obtain calcium titanium ore bed.Concentration for 10mg/ml PBDTTT-E-T and IEICO presses D:A compares 1:1.25 are dissolved in chlorobenzene, and 70 DEG C of heating stirrings obtain organic polymer layers precursor solution in 5 hours.Should Precursor solution to be deposited in 1300rpm spin coatings 60s condition again glove box on calcium titanium ore bed, then 100 DEG C annealing 10min Had and polymer light absorbed layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does electrode for 100nm Al.Gained device Part structure is FTO/PEDOT:PSS/H2C(NH2)2PbI3/PBDTTT-E-T:IEICO/Al, it is every square centimeter in 100 milliwatts Open-circuit voltage is 0.63V under simulated solar light irradiation, and short circuit current flow is 5.8mA/cm2, fill factor, curve factor is 47.4%, conversion efficiency For 1.73%.Fig. 8 gives the device under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts The EQE curves of current -voltage curve and the device.
Embodiment 8
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By PEDOT:PSS with after the filtering of 0.45um filter with 3000rpm rotating speed It is spun on electro-conductive glass, 150 DEG C of annealing 15min obtain hole transmission layer.By PbI2:DMSO=1:1 is dissolved in DFM (N, N- bis- NMF) in solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on PEDOT:PSS hole transmission layers Upper rotating speed is 5000rpm, then 70 DEG C of annealing 10min.Then by 68mg/ml H2C(NH2)2I aqueous isopropanols are with 5000rpm Rotating speed be spun on PbI2On, 150 DEG C of annealing 30min obtain calcium titanium ore bed.The TTV2 and PC that concentration is 10mg/ml70BM is pressed D:A compares 1:1.5 are dissolved in chloroform:O-dichlorohenzene=4:1 in the mixed solvent, stirring obtains organic polymer layers precursor in 5 hours Solution.The precursor solution is had and gathered to be deposited in 1800rpm spin coatings 30s condition again glove box on calcium titanium ore bed Compound light absorbing layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does electrode for 100nm Al.Obtained device structure is FTO/PEDOT:PSS/H2C(NH2)2PbI3/TTV2:PC70BM/Al, in 100 milliwatts simulated solar light irradiation every square centimeter Lower open-circuit voltage is 0.69V, and short circuit current flow is 7.5mA/cm2, fill factor, curve factor is 18.6%, and conversion efficiency is 0.96%.Fig. 9 gives Current -voltage curve of the device under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts is gone out With the EQE curves of the device.
Embodiment 9 (comparative example)
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:CsI=1:1 is dissolved in DFM In (DMF) solution, CsPbI is made in the HBr for adding 30~40ul/ml3Precursor concentration is 1M.Will CsPbI3 precursors are spun on TiO2Upper rotating speed is 5000rpm, 30s.Then 100 DEG C of annealing 10min obtain calcium titanium ore bed.Dense Spend and be dissolved in for 72.3mg/ml Spiro-OMeTAD in chlorobenzene, 1ml solution addition 29ul tetra-terts pyridine and 17.5ul Li-TFSI/ acetonitriles (520mg/ml) solution.The Spiro-OMeTAD solution is deposited on calcium with 3000rpm spin coatings 30s condition On titanium ore layer, then 100 DEG C of annealing 10min are had and polymer light absorbed layer.Finally in 1x10-4Below Pa vacuum evaporations are thick Spend and do positive pole for 100nm Au.Obtained device structure is FTO/TiO2/CsPbI3/ Spiro-OMeTAD/Au, it is every in 100 milliwatts Open-circuit voltage is 0.86V under the simulated solar light irradiation of square centimeter, and short circuit current flow is 14.5mA/cm2, fill factor, curve factor is 43.1%, conversion efficiency is 5.4%.Figure 10 gives the device without light irradiation and through 100 milliwatts mould every square centimeter Intend the EQE curves of the current -voltage curve and the device under sunshine irradiation.
Embodiment 10
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in In DFM (DMF) solution, it is 1M that PbI2 precursors concentration, which is made,.PbI2:CsI=1:1 is dissolved in DFM (N, N- Dimethylformamide) in solution, adding 30~40ul/ml HBr, CsPbI3 precursors concentration is made is 1M.By body before CsPbI3 Body is spun on TiO2Upper rotating speed is 5000rpm, 30s.Then 100 DEG C of annealing 10min obtain calcium titanium ore bed.It is 10mg/ concentration Ml PBDTTT-E-T and IEICO presses D:A compares 1:1.25 are dissolved in chlorobenzene, and 70 DEG C of heating stirrings obtain organic polymer in 5 hours Layer precursor solution.By the precursor solution to be deposited in 1300rpm spin coatings 60s condition again glove box on calcium titanium ore bed, Then 100 DEG C of annealing 10min are had and polymer light absorbed layer.Finally in 1x10-4Below Pa vacuum evaporations thickness is 100nm Au do positive pole.Obtained device structure is FTO/TiO2/CsPbI3/PBDTTT-E-T:IEICO/Au, in every square li of 100 milliwatt Open-circuit voltage is 0.62V under the simulated solar light irradiation of rice, and short circuit current flow is 10.9mA/cm2, fill factor, curve factor is 48.4%, is turned It is 3.3% to change efficiency.Figure 11 gives the device without light irradiation and through the simulated solar illumination every square centimeter of 100 milliwatts The EQE curves of current -voltage curve and the device under penetrating.
Embodiment 11 (comparative example)
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in In DFM (DMF) solution, it is 1M that PbI2 precursors concentration, which is made,.By PbI2Precursor is spun on TiO2It is upper to turn Speed is 5000rpm, then by 50mg/ml CH3NH3I//aqueous isopropanol is spun on PbI with 5000rpm rotating speed2On, 100 DEG C annealing 30min obtain calcium titanium ore bed.Concentration is dissolved in chlorobenzene for 72.3mg/ml Spiro-OMeTAD, the addition of 1ml solution Li-TFSI/ acetonitriles (520mg/ml) solution of 29ul tetra-terts pyridine and 17.5ul.By the Spiro-OMeTAD solution with 3000rpm spin coatings 30s condition is deposited on calcium titanium ore bed, and then 100 DEG C of annealing 10min are had and polymer light absorbs Layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does positive pole for 100nm Au.Obtained device structure is FTO/TiO2/ CH3NH3PbI3/ Spiro-OMeTAD/Au, open-circuit voltage is under 100 milliwatts simulated solar light irradiation every square centimeter 0.98V, short circuit current flow is 19.5mA/cm2, fill factor, curve factor is 66.2%, and conversion efficiency is 12.7%.Figure 12 gives the device Current -voltage curve and the device under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts EQE curves.
Embodiment 12
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in DFM In (DMF) solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on TiO2Upper rotating speed is 5000rpm, then by 50mg/ml CH3NH3I//aqueous isopropanol is spun on PbI with 5000rpm rotating speed2On, 100 DEG C are moved back Fiery 30min obtains calcium titanium ore bed.Concentration is pressed D for 10mg/ml PBDTTT-E-T and IEICO:A compares 1:1.25 it is dissolved in chlorobenzene In, 70 DEG C of heating stirrings obtain organic polymer layers precursor solution in 5 hours.By the precursor solution with 1300rpm spin coatings 60s Condition be deposited on again on calcium titanium ore bed in glove box, then 100 DEG C of annealing 10min are had and polymer light absorbed layer.Most Afterwards in 1x10-4Below Pa vacuum evaporations thickness does positive pole for 100nm Au.Obtained device structure is FTO/TiO2/ CH3NH3PbI3/PBDTTT-E-T:IEICO/Au, open-circuit voltage is under 100 milliwatts simulated solar light irradiation every square centimeter 0.91V, short circuit current flow is 20.3mA/cm2, fill factor, curve factor is 53.6%, and conversion efficiency is 9.9%.Figure 13 gives the device Current -voltage curve and the device under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts EQE curves.
Embodiment 13
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in DFM In (DMF) solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on TiO2Upper rotating speed is 5000rpm, then by 50mg/ml CH3NH3I//aqueous isopropanol is spun on PbI with 5000rpm rotating speed2On, 100 DEG C are moved back Fiery 30min obtains calcium titanium ore bed.The TTV2 and PC that concentration is 10mg/ml70BM presses D:A compares 1:1.5 are dissolved in chloroform:O-dichlorohenzene =4:1 in the mixed solvent, stirring obtains organic polymer layers precursor solution in 5 hours.By the precursor solution with 1800rpm Spin coating 30s condition is deposited on calcium titanium ore bed in glove box again to be had and polymer light absorbed layer.Finally in 1x10-4Pa with Lower vacuum evaporation thickness does positive pole for 100nm Au.Obtained device structure is FTO/TiO2/CH3NH3PbI3/TTV2:PC70BM/ Au, open-circuit voltage is 0.8V under 100 milliwatts simulated solar light irradiation every square centimeter, and short circuit current flow is 12mA/cm2, fill out It is 26.1% to fill the factor, and conversion efficiency is 2.5%.Figure 14 gives the device without light irradiation and through 100 every square of milliwatts Centimetre simulated solar light irradiation under current -voltage curve and the device EQE curves.
Embodiment 14 (comparative example)
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in In DFM (DMF) solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on TiO2It is upper to turn Speed is 5000rpm, then 70 DEG C of annealing 10min.Then by 68mg/ml H2C(NH2)2I aqueous isopropanols are turned with 5000rpm's Speed is spun on PbI2On, 150 DEG C of annealing 30min obtain calcium titanium ore bed.Concentration is dissolved in for 72.3mg/ml Spiro-OMeTAD In chlorobenzene, 1ml solution addition 29ul tetra-terts pyridine and 17.5ul Li-TFSI/ acetonitriles (520mg/ml) solution.Should Spiro-OMeTAD solution is deposited on calcium titanium ore bed with 3000rpm spin coatings 30s condition, and then 100 DEG C of annealing 10min are obtained Have and polymer light absorbed layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does positive pole for 100nm Au.Obtained device knot Structure is FTO/TiO2/H2C(NH2)2PbI3/ Spiro-OMeTAD/Au, in 100 milliwatts simulated solar light irradiation every square centimeter Lower open-circuit voltage is 1.04V, and short circuit current flow is 22.9mA/cm2, fill factor, curve factor is 65.9%, and conversion efficiency is 15.7%.Figure 15 Give current-voltage of the device under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts bent The EQE curves of line and the device.
Embodiment 15
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in DFM In (DMF) solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on TiO2Upper rotating speed is 5000rpm, then 70 DEG C annealing 10min.Then by 68mg/ml H2C(NH2)2I aqueous isopropanols are revolved with 5000rpm rotating speed It is applied to PbI2On, 150 DEG C of annealing 30min obtain calcium titanium ore bed.Concentration is pressed D for 10mg/ml PBDTTT-E-T and IEICO:A Than 1:1.25 are dissolved in chlorobenzene, and 70 DEG C of heating stirrings obtain organic polymer layers precursor solution in 5 hours.By the precursor solution To be deposited in 1300rpm spin coatings 60s condition again glove box on calcium titanium ore bed, then 100 DEG C of annealing 10min are had and gathered Compound light absorbing layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does positive pole for 100nm Au.Obtained device structure is FTO/TiO2/H2C(NH2)2PbI3/PBDTTT-E-T:IEICO/Au, in 100 milliwatts simulated solar light irradiation every square centimeter Lower open-circuit voltage is 0.84V, and short circuit current flow is 25mA/cm2, fill factor, curve factor is 48.4%, and conversion efficiency is 10.2%.Figure 16 gives Current -voltage curve of the device under the simulated solar light irradiation every square centimeter without light irradiation and through 100 milliwatts is gone out With the EQE curves of the device.
Embodiment 16
Sputtering there is into doping fluorine SnO2(FTO) transparent conducting glass uses liquid detergent, running water, deionized water, third successively Ketone, isopropanol are cleaned by ultrasonic twice, nitrogen drying.By 0.15M titanium acetylacetone/butanol solution with 2000rpm rotating speed It is spun on electro-conductive glass, 125 DEG C of annealing 5min, then 50nm TiO2Slurry with ethanol dilute 6 times, with 4500rpm's Then 550 DEG C of sintering 30min of substrate are obtained TiO by rotating speed spin coating 20s2Electron transfer layer.By PbI2:DMSO=1:1 is dissolved in DFM In (DMF) solution, PbI is made2Precursor concentration is 1M.By PbI2Precursor is spun on TiO2Upper rotating speed is 5000rpm, then 70 DEG C annealing 10min.Then by 68mg/ml H2C(NH2)2I aqueous isopropanols are revolved with 5000rpm rotating speed It is applied to PbI2On, 150 DEG C of annealing 30min obtain calcium titanium ore bed.Concentration is pressed D for 10mg/ml TTV2 and PC70BM:A compares 1: 1.5 are dissolved in chloroform:O-dichlorohenzene=4:1 in the mixed solvent, stirring obtains organic polymer layers precursor solution in 5 hours.Will The precursor solution is had and polymer light to be deposited in 1800rpm spin coatings 30s condition again glove box on calcium titanium ore bed Absorbed layer.Finally in 1x10-4Below Pa vacuum evaporations thickness does positive pole for 100nm Au.Obtained device structure is FTO/TiO2/ H2C(NH2)2PbI3/TTV2:PC70BM/Au, open-circuit voltage is under 100 milliwatts simulated solar light irradiation every square centimeter 0.52V, short circuit current flow is 6.1mA/cm2, fill factor, curve factor is 19.2%, and conversion efficiency is 0.6%.Figure 17 gives the device and existed Without light irradiation and through the current -voltage curve under 100 milliwatts simulated solar light irradiation every square centimeter and the device EQE curves.
Technical scheme is described in detail above-described embodiment.It is apparent that the present invention is not limited being retouched The embodiment stated.Based on the embodiment in the present invention, those skilled in the art can also make a variety of changes accordingly, but appoint What is equal with the present invention or similar change belongs to the scope of protection of the invention.

Claims (10)

1. a kind of perovskite/organic integration solar cell, it is characterised in that its structure includes from bottom to top：Transparency electrode (1), Charge transport layer (2), perovskite light absorbing layer (3), organic light absorbing layer (4) and metal electrode (5).
2. a kind of perovskite/organic integration solar cell according to claim 1, it is characterised in that described electric charge is passed Defeated layer is electron transfer layer or hole transmission layer.
3. a kind of perovskite/organic integration solar cell according to claim 2, it is characterised in that the device architecture For transparency electrode/electron transfer layer/perovskite light absorbing layer/organic light absorbing layer/hole transmission layer/metal electrode；Or it is transparent Electrode/hole transmission layer/perovskite light absorbing layer/organic light absorbing layer/electron transfer layer/metal electrode.
4. a kind of perovskite/organic integration solar cell according to claim 1, it is characterised in that described organic light The absorption spectrum of absorbed layer is wider than the absorption spectrum of perovskite light absorbing layer, is organic narrow band gap class material.
5. a kind of perovskite/organic integration solar cell according to claim 2, it is characterised in that when the electric charge is passed When defeated layer (2) is electron transfer layer, described metal electrode (5) is high work function metal；When the charge transport layer (2) is hole During transport layer, described metal electrode (5) is low work function metal.
6. a kind of preparation method of perovskite/organic integration solar cell, method one comprises the following steps：
A. transparent conductive metal oxide anode layer is prepared：The sputtered metal oxide on the substrate of glass or polyester film, is obtained To transparent conductive metal oxide anode layer；
B. hole transmission layer is prepared：The transparent conductive metal oxide anode layer that step a is obtained through ultraviolet-ozone surface at The organic material or metal oxide of spin coating high work content, hole transmission layer is obtained through thermal annealing after reason；
C. perovskite light absorbing layer is prepared：Lead source and iodide are dissolved in solvent, heating stirring obtains perovskite precursor molten Liquid, the solution is spun on the hole transmission layer that step b is obtained, perovskite light absorbing layer is obtained through thermal annealing；
D. organic light absorbing layer is prepared:P-type organic material and N-type organic material are mixed in proportion and is dissolved in solvent solution is made, The solution is spun on calcium titanium ore bed and obtains organic light absorbing layer；
E. electron transfer layer is prepared：Low work content is prepared by the method for spin coating or evaporation on organic light-absorption layer that step d is obtained Organic or metal oxide electron transport layer；
F. cathode layer is prepared：Vacuum evaporation metal electrode, is used as cathode layer on the electron transfer layer that step e is obtained；
Method two comprises the following steps：
A. transparent conductive metal oxide anode layer is prepared：The sputtered metal oxide on the substrate of glass or polyester film, is obtained To transparent conductive metal oxide-coated cathode layer；
B. electron transfer layer is prepared：By n-type metal oxide it is spin-coated or be sprayed at transparent conductive cathode layer on, through high annealing After obtain electron transfer layer；
C. perovskite light absorbing layer is prepared：Lead source and iodide are dissolved in solvent, heating stirring obtains perovskite precursor molten Liquid, the solution is spun on the electron transfer layer that step b is obtained, perovskite light absorbing layer is obtained through thermal annealing；
D. organic light absorbing layer is prepared:P-type organic material and N-type organic material are mixed in proportion and is dissolved in solvent solution is made, The solution is spun on calcium titanium ore bed and obtains organic light absorbing layer；
E. hole transmission layer is prepared：Original text work content is prepared by the method for spin coating or evaporation on organic light-absorption layer that step d is obtained Organic or metal oxide hole transmission layer；
F. anode layer is prepared：Vacuum evaporation metal electrode, is used as anode layer on the hole transmission layer that step e is obtained.
7. preparation method according to claim 6, it is characterised in that organic material is described in the step b of method one PEDOT：PSS.
8. preparation method according to claim 6, it is characterised in that by PbI in method one or illegal two steps c2:DMSO Mass ratio is 1:1, DMF concentration is dissolved in for 1M, and spin coating rotating speed is 5000rpm, CH3NH3I or H2C(NH2)2I aqueous isopropanol is dense Degree is respectively 50mg/ml and 68mg/ml, and spin coating rotating speed is 5000rpm；Or by PbI21 is pressed with CsI:Before 1 ratio is mixed to prepare Body solution, then 100 DEG C of annealing obtain CsPbI after a step spin-coating method3Perovskite light absorbing layer.
9. preparation method according to claim 6, it is characterised in that in method one or the step d of method two by TTV2 with PC70BM than mixing by necessarily solvent is dissolved in, and the solvent is chloroform and o-dichlorohenzene, or PBDTTT-E-T is pressed with IEICO Necessarily solvent being dissolved in than mixing and precursor solution being made, the solvent is chlorobenzene, and resulting solution is spun on into what step c was obtained Organic polymer light absorbing layer is obtained on calcium titanium ore bed.
10. preparation method according to claim 6, it is characterised in that by 0.15M titanium acetylacetones in the step b of method two N-butanol be spun in transparency electrode, 125 DEG C annealing 5~10min, be then spin coated onto TiO2Casing play solution, then by 550 DEG C sintering 30min prepare TiO2Electron transfer layer.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807676A (en) * 2018-05-16 2018-11-13 暨南大学 Wide spectrum based on organic photoactive layers responds inorganic perovskite solar cell and its preparation method and application
JP2019212763A (en) * 2018-06-05 2019-12-12 住友化学株式会社 Photoelectric conversion element
CN109378385A (en) * 2018-10-08 2019-02-22 电子科技大学 A kind of organic perovskite combination solar battery based on full spectral absorption
CN111063804A (en) * 2018-10-17 2020-04-24 国家纳米科学中心 Perovskite light absorption layer film, preparation method thereof and solar cell using perovskite light absorption layer film
CN109585660A (en) * 2018-12-07 2019-04-05 吉林大学 A kind of perovskite photodetector and preparation method thereof based on the double passivation layers of organic inorganic hybridization
CN115536058A (en) * 2022-09-19 2022-12-30 上海钙晶科技有限公司 Method for reducing band gap of perovskite thin film by introducing iodine three anions through secondary annealing
CN115536058B (en) * 2022-09-19 2023-12-05 上海钙晶科技有限公司 Method for reducing perovskite film band gap by introducing iodine triple anions through secondary annealing

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